ATALANTE Basic physico-chemistry

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1 ATALANTE 200 Basic physicochemistry Lanthanide and actinide inorganic complexes in natural waters. TRLFS* and ESIMS** studies. Advances in acquisition of thermodynamic data * TimeResolved Laserinduced Fluorescence Spectroscopy ** ElectroSpray Ionization Mass Spectrometry Thomas VERCOUTER,2,3, Badia AMEKRAZ 2,3, Christophe MOULIN 3, Pierre VITORGE 2,3 ANDRA National radioactive waste management agency 2 UMR 8587 (Evry University CEA CNRS) 3 Nuclear Energy Division/ Department of Physics and Chemistry Service for the studies of the radionuclides behaviour Molecules and Radionuclides Speciation Laboratory June 225, 200

2 Advances in acquisition of thermodynamic data Sulphate complexation ESIMS (La) TRLFS (Eu) Carbonate complexation TRLFS and solubility measurements (Eu) 3 Temperature influence on carbonate complexation TRLFS (Cm) June 225, 200 2

3 Formation of LaSO : an ESIMS study % La has a very stable oxidation state III The speciation in the initial solution with ph =2 can be simply described La 3 (aq) SO (aq) = LaSO (aq) Liquid phase Gas phase [LaO(H 2 [La(SO )(H 2 [La(SO )(HNO 3 )(H 2 [La(OH)(H [La(NO 3 (H [La(SO )(H 2 SO ) m (H 2 [LaO(HNO 3 ) m/z K [LaSO (aq) = 3 2 [La (aq) [SO (aq) Numerous La(III) species in the gas phase (positiveion detection mode) Interpretation : identification with the species in the aqueous solution June 225, 200 3

4 Stabilities of MSO and M(SO ESIMS TRLFS La 3 (aq) SO (aq) = LaSO (aq) Eu 3 SO = EuSO EuSO SO = Eu(SO ) 2 lg ([LaSO / [La 3 ) La(SO (aq) NaClONa2SO /Na 2.5<I m <2.2 2 ph 2 ph I FLUO (a.u.) NaClONa2SO /Na 2 0.5< I m <0.9 HClOH2SO /H 2 I m < Slope 0.0 < Ionic strength < lg [SO lg K (La) = 2.95 ± 0.5 % Eu EuSO 0 20 Eu(SO ) 2 0 Ionic strength < 0.02 lg [SO lg K (Eu) = 3.0 ± 0. lg [SO lg K 2 (Eu) = 2.2 ± 0. lg K and lg K 2 dependences with ionic strength, I m June 225, 200

5 Comparison with selected literature data OECDNEA critical reviews 995 R.J. SILVA, G. BIDOGLIO, M.H. RAND, P.B. ROBOUCH, H. WANNER, I. PUIGDOMENECH, Chemical thermodynamics of Am, Elsevier Science, Amsterdam, 37p update R. GUILLAUMONT, T. FANGHANEL, V. NECK, J. FUGER, D.A. PALMER, I. GRENTHE, M.H. RAND, Update on the chemical thermodynamics of U, Np, Pu, Am and Tc, Elsevier Science, Amsterdam, 99p. An 3 SO = AnSO An 3 2 SO = An(SO Ion exchange or solvent extraction (NaClO Na 2 SO ) ESIMS La (HNO 3 H 2 SO ) TRLFS Eu (NaClO Na 2 SO ) Ion exchange or solvent extraction (NaClO Na 2 SO ) TRLFS (NaClNa 2 SO ) TRLFS (NaClNa 2 SO ) P. PAVIET, T. FANGHANEL et al., Radiochim. Acta, 7, 9903 (996) V. NECK, T. FANGHANEL et al., Report, 08 (998) June 225, 200 5

6 Carbonate complexation of M(III) lg K3 lg K2 lg K M 3 MCO 3 M(CO 3 M(CO 3 ) 3 3 Série Eu(III) Eu2 Eu 3 Am(III) Am2 Am 3 Cm(III) Cm2 Cm I m (mol.kg H2O ) Data Base (OECDNEA) Analogy between M(III), but discrepancies in lg K i values for M(CO 3 ) i 32i with M = Eu, Am, Cm systematic errors (differences in the techniques, ph measurements, control of CO 2 (g), [HCO 3 and [CO 3,...) difficulties in the interpretations of experimental data (nature of solid phases, sensitivity analyses, ) Limiting carbonate complex M(CO 3 ) 3 3 and/or M(CO 3 ) 5? Analogy? June 225, 200 6

7 Planning of TRLFS experiments on Eu solutions lg [H I FLUO (a.u.) Am(OH AmOH 2 Am 3 3,5 2 lg P CO2 =0 Am(OH) 3 (aq) Am2(CO3)3(s) AmOHCO 3 (s) Am(OH) 3 (s) AmCO 3 Am(CO 3 Am(CO 3 ) 3 3 NaAm(CO 3 (s) lg [CO λ emission (nm) lg [CO 3 Experimental conditions : control of the carbonate speciation formation of Eu carbonate complexes [Eu < solubility limit soluble species solid compounds Na 2 CO 3 NaHCO 3 / Na 2 CO 3 NaHCO 3 CO 2 (g) atm [Am=0 M ionic strength 0.M Analysis of fluorescence spectra June 225, 200 7

8 Sensitivity analysis Intensity ratio (68nm/592nm) 6 3 Fitting compwith 3 complexes 5 Fitting compwith complexes Na2CO3 2 3 I=3M Na2CO3 2 3 I>0, 3 HCO3/CO3 NaHCO 3 / Na 2 CO 3 NaHCO % CO 2 (g) CO2 atm lg [CO 3 High ionic strength (3M) : unique species lg[h Possible formation of Eu(OH or Eu(CO 3 ) i (OH) 32ij j? 8 Am(OH) 3 (aq) Am(OH Am(CO 3 Am(CO 3 ) lg [CO 3 Characterization of the formation of EuCO 3, Eu(CO 3 ), Eu(CO 3 ) 3 3 ( Eu(CO 3 ) 5? ) Sensitivity analysis : possible other complexes Isolation of the limiting complex at high ionic strength Stoichiometry of the limiting complex is not straightforward June 225, 200 8

9 Limiting complex Eu(CO 3 ) 3 3 Solubility experiments at high ionic strength : synthesis of NaEu(CO 3,xH 2 O(s) (confirmed by XRD) [Eu measured by ICPAES NaEu(CO 3,xH 2 O(s) (i2) CO 3 = Na Eu(CO 3 ) 32i i xh 2 O lg m(na )lg m(eu) 6D ε m(na ) [Na=M [Na=3M [Na=2M lg m(co 3 ) lg m(na )lg m(eu) Slope Slope analysis => i = 3 thus Eu(CO 3 ) 3 3 Ionic strength corrections good agreement between the data at different [Na no Eu(CO 3 ) 5 is observed up to [CO 3 = 2M Influence on other lg K values June 225, 200 9

10 T dependence on Cm(CO 3 ) i 32i formation TRLFS on 28 Cm solutions from 0 C to 70 C effect of T on the fluorescence lg K i by spectral decomposition I FLUO (a.u.) 0 C 20 C 25 C 37 C 50 C Cm(III) in Na 2 CO 3 M determination of thermodynamic constants R ln K R ln K T (J.mol.K ) T R ln K = T H( r T ) T λ emission (nm) Cm(CO 3 ) CO 3 = Cm(CO 3 ) 3 3 Linear regression ( ±.96 σ ) r H = ± kj.mol R ln K 25 C = 32 ± J.mol.K r G 25 C = 9.5 ± 0.3 kj.mol (K ) T r S 25 C = 30 ± J.mol.K June 225, 200 0

11 Acknowledgments Eric Giffaut (ANDRA) Michel Tabarant for ICPAES analyses, Alex Chénière for DRX analyses (CEA Saclay, DEN/DPC/SCP/LRSI) Solange Hubert for supplying a 28 Cm stocksolution (IPN, Orsay) People of SECR and SCP June 225, 200

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